DE3614099C2 - - Google Patents

Description

Laminate with dirt-repellent surface, Process for its preparation and its Use as wallcovering.

The invention relates to vinyl chloride polymer laminates and carrier-free Layers with improved dirt-repellent texture.

Laminates based on synthetic polymers are known. So describes US-PS 30 41 222 a book cover material in which the base fabric with a layer of vinyl copolymers, butanol-modified urea Formaldehyde resin and alkyd resin is coated on the ink brought with a layer of Vinylchloridcopolymerem and Polyvinyl chloride is covered. DE-OS 29 38 051 describes a wall cladding with an outer layer of polyethylene terephthalate, Polytetrafluoroethylene or urethane / polyester copolymer.

The object of the invention is in contrast the provision of vinyl Chloride polymer laminates and carrier-free layers with improved dirt-repellent texture as well Process for producing such laminates. Fiction According to a layer of a flexible vinyl chloride polymer with a catalyzed, solvent-containing Mass of a reactive polyester and an amino resin Coated and heated to provide hardening and adhesion Resin on the vinyl chloride polymer layer under removal tion of the solvent and a flexible Vinyl chloride polymer layer to provide a has dirt-repellent texture or slightly un The removal of stains can be cleaned.

The drawing represents a flow diagram, the procedure for the preparation of stain-resistant vinyl chloride polymer (PVC) laminates or carrier-free layers explained.  

As is apparent from the drawing, the preferred embodiments The invention is explained, is a vinyl chloridpolymer plastisol applied and melted or a plasticized vinyl chloride polymer composition becomes kalan drilled or extruded. These products can work on one Substrate or a substrate can be applied. In both cases, the vinyl chloride polymer layer (about 0.025 to 0.76 mm (1 to 30 mils) once or be printed several times. Subsequently, the be printed layer embossed, possibly reprinted and finally  with a layer of a solution of a reactive Polyester resin-amino resin composition coated and hardened, a vinyl chloride polymer layer having an outer Dirt-repellent layer of about 0.0025 to 0.051 mm (0.1 to 2 mils) thickness.

The vinyl chloride polymer may be an emulsion polymer (plastisol) or a suspension polymer. Preferably, the vinyl chloride polymer may be Homopolyvinyl chloride act or it is a Copolymer from a parent amount by weight Vinyl chloride and a minor amount by weight of one copolymerizable monomers from the group vinyl acetate, Vinylidene chloride and maleic acid ester. It can too Bulk and solution polymers of vinyl chloride used become. Furthermore, mixtures of vinyl chloride polymers be used. Vinyl chloride polymers and copolymers are known. In this regard, for example, on following publications referenced: Vinyl and Related Polymers, Schildknecht, John Wiley & Sons, Inc., New York, 1952; Sarvetnick, Polyvinyl Chloride, Van Nostrand Reinhold Company, New York, 1969; Sarvetnick, Plastisols and Organosols, Van Norstrand Reinhold Company, New York, 1972; and Modern Plastics Encyclopedia, 1980-1981, October 1980, Vol. 57, No. 10A, McGraw-Hill, Inc., New York.

The amount of plasticizer used, the vinyl chloride can make polymer flexible from 30 to 100 weight divide per 100 parts by weight of the total vinyl chloride vary polymer resin. For example, for usable soft butyl octyl phthalate, dioctyl phthalate, hexyl decyl phthalate, dihexyl phthalate, diisooctyl phthalate, di capryl phthalate, di-n-hexyl azelate, diisononyl phthalate, di octyl adipate, dioctyl sebacate, trioctyl trimellitate, triiso octyl trimellitate, triisononyl trimellitate, isodecyldiphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, polymers  Plasticizer, epoxidized soybean oil, octylepoxy tallate, isooctylepoxytallate and the like. It can also Softener mixtures are used.

The vinyl chloride polymer compositions are preferably further Compounding components for vinyl chloride polymers einver leibt. Examples of such ingredients are silicon oxide products, such as precipitated silica, colloidal silica, calcium silicate and the like., Calcium carbonate, UV absorbers, fungicides, carbon black, barytes, Barium-cadmium-zinc stabilizers, barium-cadmium stabilizers dispersants, tin stabilizers, dibasic lead phosphite, Sb₂O₃, zinc borate and the like. And mixtures of these products. Pigments based on TiO₂, red iron oxide, phthalo cyanine blue or green or other colored pigments be used. The pigments and the remaining dry Additives are preferably softened in one or more They are dispersed or dissolved before they are mixed Vinyl chloride polymer compositions may be added. These Compounding ingredients are used in effective amounts by weight used to paint, mold, stabilization, viscosity and the like of the plasticized vinyl chloride polymer check.

The vinyl chloride polymer composition may be suitable propellant or Containing foaming agents, such as sodium bicarbonate and organic agents, e.g. 1,1'-azobisformamide, 4,4'-oxy bis (benzenesulfonylhydrazide), p-toluenesulfonylhydrazide and the like. To melt layers of cellular or foamed vinyl chloride polymer compositions. at the propellants may require an activator. Such propellants are known.

Furthermore, in the masses mixing or drawing resins for Vinyl chloride polymers in subordinate (relative to  vinyl chloride polymer compositions).

The components for forming the vinyl chloride polymer masses can be mixed in any variety presented and mixed, for. In horse Planetary mixers, Hobart dough mixers, Banbury mixers, Rubber two-roll mixers, Nauta mixers, ribbon blenders and the like

The vinyl chloride polymer composition can become layers or films be formed, the carrier-free or preferably with a substrate are provided. When using a Vinyl chloride polymer plastisol composition can be applied to a Dividing surface is poured and heated to form a Films are melted. When using a weichge made suspension vinyl chloride polymer composition can this calendered or extruded to form a film and be melted. Temperatures can be from about 93 to 204 ° C (200 to 400 ° F). Preferably, in in both cases, the compounded vinyl chloride polymer compositions applied to substrates or have a back on. In the case of applied to a substrate Vinyl chloride polymer compositions may be present in the substrate (Support) to tissue products (Drell, gauze, gauze and dergl.), knitted or knitted textile materials, Paper and the like act. The textile materials can made of cotton, cellulose, nylon, polyester, aramid, Rayon or acrylic fibers or threads (strings) or off Be prepared mixtures of these products. In some Cases may require the textile material with an adhesive coating or adhesive bath act to increase liability or better adhesion between To ensure tissue and vinyl chloride polymer composition.

The provided with a substrate or carrier-free Layer or film of vinyl chloride polymer composition  preferably on the surface of the vinyl chloride polymer with a for the coloration of vinyl chloride ge suitable printing ink printed to pattern and as desired to produce the same. Such printing inks are known and can be applied by different printing methods, z. B. by gravure printing, flexographic printing, screen printing, jet printing, Rotary printing and the like; see. Modern Plastics Encyclo pedia, 1980-1981, pp. 464-465. The printing process can be up to be repeated five or more times to become a varia tion of colors and patterns, with the individual Pressure levels each at about 65 to 74 ° C. be performed.

The applied to a substrate or carrier-free, printed or unprinted layer or film of vinyl chloride composition preferably subjected to an embossing process to the vinyl To structure the chloride layer and to suitable for aesthetic or functional purposes or get structures. The embossing of thermoplastic Films, layers or foils are known and will Usually carried out by placing the film under kon trolled preheating and precooling conditions go through between an embossing roller and a support roller leaves; see. Modern Plastics Encyclopedia, 1980-1981, pp. 454-455. Other decorating and printing may occasionally be carried out by the aforementioned pressure colors on the embossed surface of the vinyl chloride polymer applying, for example, a more favorable aesthetic Appearance can be caused.

The reactive polyester resin amino resin for use as outer layer on the vinyl chloride polymer layer becomes from a solution of a reactive polyester (Alkyd resin) and an amino resin in an organic  Solvent, such as methyl ethyl ketone, which is a catalyst contains, manufactured and at temperatures of at least about 93 ° C applied to a cure and Ver wetting of the alkyd resin and the amino resin. The solvent-containing mass of reactive polyester Resin and amino resin can be applied directly to the layer from the Vinyl chloride polymer composition (with or without back or layer carrier) are applied, the printing and / or Embossing stage are provided or not. Preferably the catalyst-containing solution of the reactive polyester and Amino resin on an embossed and printed, compounded and plasticized vinyl chloride polymer composition based on a suitable substrate or substrate, applied.

The polyester resins (alkyd resins) are formed by a condensate sationspolymerisationsreaktion, generally under Er warm in the presence of a catalyst, a mixture a polybasic acid and a polyhydric alcohol manufactured. Monobasic oils or fatty acids, monohydroxy alcohols and anhydrides may be present. It can also contain active hydrogen atoms, for. B. Carbon acid groups for the reaction with the amine resin. Examples for acids for use in the formation of alkyd resins or reactive polyesters are adipic acid, azelaic acid, Seba cinic acid, terephthalic acid, phthalic anhydride and the like Examples of polyhydric alcohols are ethylene glycol, Pro pylene glycol, diethylene glycol, dipropylene glycol, glycerol, Butylene glycol, 2,2-dimethyl-1,3-propanediol, trimethylol propane, 1,4-cyclohexanedimethanol, pentaerythritol, trimethyl Loläthan and the like. Mixtures of polyols and polycarbon acids can be used. For example, as reactive polyester, the condensation product of tri methylolpropane, 2,2-dimethyl-1,3-propanediol, 1,4-cyclo hexanedimethanol, phthalic anhydride and adipic acid ver  be used. It can also be mixtures of these reactive Polyester or alkyd resins are used. alkyd resins are for example from the following publications be known: Encyclopaedia of Polymer Science and Technology, Vol. 1 (1964), John Wiley & Sons, Inc., pp. 663-734; alkyd Resins, Martens, Reinhold Publishing Corporation, New York, 1961; and Alkyd Resin Technology, Patton, Interscience Publishers, John Wiley and Sons, New York, 1962. Unsatisfied Polybasic acids and unsaturated polyols can be used in the Condensation reaction to some extent but are generally undesirable. The reactive one Polyester or the alkyd resin are in general to Amino resin in the form of a solution or suspension in one organic solvents, for. B. a mixture of a Ketone and an alkyl acetate, at a solids content of 60 to 80 percent, given.

In the reaction with the reactive polyester to be reacted amino Resin is, for example, alkylated benzo guanamine-formaldehyde, alkylated urea-formaldehyde or preferably alkylated melamine-formaldehyde resins. Mixtures of these resins can also be used. at for the modification of benzoguanamine-formaldehyde, urine fabric-formaldehyde or melamine-formaldehyde resins ver Alcohol used may be, for example, n-butanol, n-propanol, isopropanol, ethanol, methanol and the like. act. Such amino resins are known; see. example Aminoplastics, Vale et al., Iliffe Books Ltd., London, 1964; Amino Resins, Blair, Reinhold Publishing Corporation, New York, 1959; Modern Plastics Encyclopedia, 1980-1981, Pp. 15, 16 and 25; Encyclopedia of Polymer Science and Technology, John Wiley & Sons, Inc., Vol. 2 (1965), pp. 1-94.

Sufficient amounts by weight of the reactive polyester and of the amino resin are used to provide a dirt repellent, crosslinked layer of good resistance and flexi  stability, which is good for curing and curing the com pounded and plasticized vinyl chloride polymer layer liable to guarantee. These materials are included Temperatures of at least about 93 ° C for a sufficient time in the presence of a subordinate Weight of an acidic catalyst, such as boric acid, Phosphoric acid, acid sulfates, hydrochlorides, phthalic acid Anhydride or phthalic acid, oxalic acid or their ammonium salts, sodium or barium ethyl sulfates, aromatic Sul fatty acids such as p-toluenesulfonic acid (preferred) and the like, hardened. Before curing, the mixture can be removed from the reak tive polyester and the amino resin with matting agents or other additives.

The stain-resistant laminates according to the invention are suitable especially for wallcoverings, preferably in Hospitals. However, these can be dirt repellent Laminates also for the production of tablecloths, shoe shingles, outsides of luggage, upholstery, Interior of vehicles and seats, golf bags, other sporting goods and the like are used.

Hereinafter, the invention will become more apparent by way of examples explained.

Example 1

Homopolyvinyl chloride (PVC), the plasticizer, Stabilisa Toren and other compounding agents is included about 177 ° C on a cotton and polyester blend Drellgewebe to form a plasticized and kom pounded PVC film of about 0.102 mm (4 mils) thick on the Calf ragged tissue. Subsequently, the PVC Layer printed five times, taking between each Printing is heated to about 71 ° C. On  This creates a printed surface of the PVC film. The printed film is then under an embossing roll through led and cooled, creating an embossed pattern on the receives printed PVC film. The embossed and printed PVC film is then by means of a gravure roll with a Solution of a reactive polyester (alkyldharz) with a Content of carboxylic acid groups and an amino resin coated and at about 93 ° C to remove the solvent and formation of a dirt-repellent, networked and adhesive layer of about 0.013 mm (0.5 mil) thick Layer on the embossed and printed PVC layer ge hardened.

The mixture of the reactive polyester and the amino resin contains the following components:

ingredients weight Reactive polyester resin 80% resin, 20% solvent (mixture of methyl isobutyl ketone and n-butyl acetate)]. The polyester resin is the condensation reaction product of 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, trimethylolpropane, phthalic anhydride and adipic acid containing active hydrogen atoms (-COOH groups) 35.0 Liquid hexane methoxymethylmelamine 13.8 p-Toluenesulfonic acid in isopropanol (40% acid, 60% alcohol) 4.4 Silica-matting agents 3.8-4.3 methyl ethyl ketone 42.5 to 43

The laminated PVC composite becomes a sample pieces cut out, with dirt or staining Treated agents and then washed to effectiveness of the coating when rubbed with various cleansers to investigate.

Table I

example 2

The procedure of Example 1 is repeated, with the Ab Change that the outer layer of the solution of reactive polyester and the amino resin not on the Embossed and printed layer of reinforced PVC film is applied. The test results are in Table II compiled.

Table II

Claims (3)

1. A laminate with dirt-repellent surface, consisting of two layers with a first, optionally ver with a fabric patch ver layer of a compounded and plasticized vinyl chloride polymer, characterized in that the adhesive on the first layer second outer layer, the crosslinking product of at least one reactive polyester resin with free carboxylic acid groups and at least one amino resin from the group alkylated benzoguanamine-formaldehyde resins, alkylated urea-formaldehyde resins and alkylated melamine-formaldehyde resins. 2. A process for the preparation of the laminate according to claim 1, characterized ge indicates that one on a first, optionally with a Fabric-backed layer of a compounded and plasticized vinyl chloride polymer, a second layer of one catalysed mixture of at least one reactive polyester resin having free carboxylic acid groups and at least an amino resin from the group alkylated benzoguanamine Formaldehyde resins, alkylated urea-formaldehyde resins and alkylated melamine-formaldehyde resins and applying the mixture to at least about 93 ° C for a cure and Networking the second layer heated sufficient time. 3. Use of the laminate according to claim 1 as a wallcovering.